Hydrostability of polybutylene terephthalate composition
View Patent ↗Disclosed is a process for the manufacture of a modified polyalkylene terephthalate such as modified polybutylene terephthalate. In particular, the process comprises employing a titanium-containing catalyst formed by the reaction product of tetraalkyl titanate and a complexing agent comprising a phosphorous, nitrogen or boron atom. The process is used to prepare modified polyalkylene terephthalates characterized by improved hydrostability, as well as compositions derived therefrom.
1. A thermoplastic composition with improved hydrostability, comprising:
0.05 percent by weight of sodium stearate;
0.04 percent by weight of a stabilizer which is pentaerythritoltetrakis(3-(3,5-di-tert butyl-4-hydroxy-phenyl-)propionate);
5 percent by weight of linear low density polyethylene;
30 percent by weight of glass fiber; and
64.91 percent by weight of a modified polybutylene terephthalate prepared from polyethylene terephthalate in the presence of 1,4-butane diol and a catalyst containing phosphoric acid (PA) and 115 ppm titanium as tetraisopropyl titanate based on the polymer weight, wherein the molar ratio of tetraisopropyl titanate: phosphoric acid is 1:0.8; wherein the catalyst is generated before being combined with polyethylene terephthalate, wherein the process for preparing the modified polybutylene terephthalate comprises:
forming a catalyst solution comprising a catalyst that is the reaction product of phosphoric acid (PA) and 115 ppm titanium as tetraisopropyl titanate based on the polymer weight, which catalyst is synthesized in situ, prior to depolymerization of the polyethylene terephthalate, by combining, at an elevated first temperature, the tetraisopropyl titanate and phosphoric acid in butanediol and/or ethylene glycol, wherein the catalyst is formed employing a tetraisopropyl titanate: phosphoric acid molar ratio of 1:0.8;
subjecting the depolymerized mixture to heat to melt residual particles of polyethylene terephthalate at an elevated third temperature higher than the second temperature to obtain a molten depolymerized mixture;
polymerizing the molten depolymerized mixture under vacuum, in the presence of butanediol added following depolymerization if not before, by subjecting the molten depolymerized mixture to vacuum under heat, optionally with distillation, at a pressure of less than 2 Torr and a temperature of 220° C. to 270° C.; and
subjecting the polymerized mixture to solid state polymerization at approximately 100 mbar (75 Torr) pressure and a temperature of approximately 200° C. for about 18 to 30 h to obtain a modified polybutylene terephthalate;
wherein:
the thermoplastic composition does not contain a chain extender or quencher; and
the thermoplastic composition has improved notched impact strength and tensile strength measured at days 2 and 5 of hydroaging at 110° C. and 100% relative humidity in a pressure cooker as compared to a thermoplastic composition comprising:
0.05 percent by weight of sodium stearate;
1.7 percent by weight of 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate;
0.04 percent by weight of a stabilizer which is pentaerythritoltetrakis(3-(3,5-di-tert butyl-4-hydroxy-phenyl-)propionate);
5 percent by weight of linear low density polyethylene;
30 percent by weight of glass fiber; and
63.21 percent by weight of a modified polybutylene terephthalate containing 115 ppm tetraisopropyl titanate and no phosphoric acid and having an intrinsic viscosity of 1.2 cm 3 /g as measured in a 60:40 phenol/tetrachloroethane.